Trimethyl orthoacetate → HCID 21997645, compound

HRID 1977111Notes

Reaction equation

HRID 1977111 reaction equation
[NH2:1][C:2]1[S:3][CH:4]=[C:5]([CH3:13])[C:6]=1[S:7]([CH2:10][C:11]#[N:12])(=[O:9])=[O:8].[C:14](OC)(OC)(OC)[CH3:15]>>[CH3:14][C:15]1[NH:1][C:2]2[S:3][CH:4]=[C:5]([CH3:13])[C:6]=2[S:7](=[O:9])(=[O:8])[C:10]=1[C:11]#[N:12]

Participants

3

Reactant 2

HCID 15050Trimethyl orthoacetateHCID 21997641HCID 21997641, compound

Product 1

HCID 21997645HCID 21997645, compound

Conditions

Temperature
0 °C

Procedure

A solution of (2-amino-4-methylthiophene-3-sulfonyl)acetonitrile (0.50 g) in trimethyl orthoacetate (1 ml) was heated at 120-130° C. for 2 h and then concentrated in vacuo at ˜50° C. for 1 h. The residue was suspended in a mixture of absolute ethanol (5 ml) and triethylamine (0.32 ml) and stirred at reflux for ½ h, then at 0° C. for ½ h and filtered. The filtrate was heated at reflux for one more hour, concentrated in vacuo, dissolved in ethyl acetate (10 ml) and extracted with 1 M NaOH (10 ml). The aqueous phase was washed with ethyl acetate (2×5 ml), cooled to 0° C. and acidified with 10 M HCl, pH being adjusted to 0-1. After stirring for 1 h at 0° C. the precipitate was collected by filtration and dried to give the title compound as a practically pure beige solid. Yield 0.09 g (16%). An analytically pure sample was obtained by recrystallization from methanol; mp 347-349° C. (decomp.); 1H-NMR(DMSO-d6) δ (ppm): 12.7 (br, 1H), 7.09 (s, 1H), 2.40 (s, 3H), 2.32 (s, 3H); 13C-NMR (DMSO-d6) δ (ppm): 153.9, 143.5, 131.5, 119.6, 116.6, 113.8, 89.6, 20.4, 15.3; IR 3226, 3030, 2903, 2227(C≡N), 1580, 1526, 1281 and 1134 (SO2). Elemental analysis, % found (calc. for C9H8N2O2S2): C 44.69 (44.98); H 3.22 (3.36); N 11.33 (11.66); S 26.76 (26.69).

Workup

  1. concentrationconcentrated in vacuo at ˜50° C. for 1 h
  2. additionThe residue was suspended in a mixture of absolute ethanol (5 ml) and triethylamine (0.32 ml)
  3. temperatureat reflux for ½ h
  4. filtrationfiltered
  5. temperatureThe filtrate was heated
  6. temperatureat reflux for one more hour
  7. concentrationconcentrated in vacuo
  8. dissolutiondissolved in ethyl acetate (10 ml)
  9. extractionextracted with 1 M NaOH (10 ml)
  10. washThe aqueous phase was washed with ethyl acetate (2×5 ml)
  11. stirringAfter stirring for 1 h at 0° C. the precipitate
  12. filtrationwas collected by filtration
  13. customdried

Sources & evidence

ORD record
ord-0760d7f187974e288bcb38bbd825db47
Source dataset
uspto-grants-2001_05
Patent number
US06232310B1

Reaction notes

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